Remedial Kinetics and Mechanism.pptVIP

CHEM 360 Spring 2004 Remedial Kinetics and Mechanism Empirical Chemical Kinetics Measurement of Reaction Rates Simple Rate Laws Second-order Kinetics: [A] ? [B] Determination of Order 1 Determination of Order 2 Data Analysis Temperature Dependence Modified by Jed Macosko ? Paul Percival conc. time A + B ? C to determine / describe / predict the course of reactions ___________: identify reactants, products, intermediatesidentify ___________reaction steps ___________: measure reaction rates ? rate constantsexplore effects of T, P, [H+], …relate rate constants to molecular propertiesdevelop theories ? make predictions Rate data (growth of products, decay of reactants) are the basic experimental input to reaction kinetics. The shapes of kinetic data plots depend on rate constants and concentrations. Their functional form ? ___________ __________dependence of reactant and product concentrations rate constant order in B total order = x + y In elementary reaction steps the orders are always integral, but they may be fractional in multi-step reactions. The ___________is the number of molecules in a reaction step. The ___________of a reaction (the advancement) In general, a chemical equation is written For an infinitesimal advancement dx the concentration of each reactant/product changes by By definition, Reaction rates usually depend on reactant ___________, Sampling of reaction mixture, followed by chemical analysis, chromatography, spectroscopy Quenching of whole reaction or sample, followed by … Matrix isolation is a particular quenching technique used to study otherwise short-lived species. Flow A B mixing chamber detector The time between mixing and measurement is varied by changing the ___________or the ___________. Real time analysis involves measurement of a quantity that varies throughout the reaction. This could be: a general property of the systempressure, volume, conductance, optical rotation, … a molecular property: usually by spectroscopy Acc